Arylamino compounds



Patented y 1, 1945 UNITED", STATES PATENT OFFICE AItYLAMINO COMPOUNDS Joseph B. Dickey and James G. McNally, Rochester, N. Y., assignors to Eastman sKodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing Application March 20, 1943,

. Serial No. 479,906

6 Claims.

This invention relates to arylamino compounds containing a phosphono group and to photographic developing agents comprising such arylamino compounds. This application is a continuation-in-part of our copending application, Serial No, 301,467, filed October 26, 1939.

It is known that oand pphenylenediami ne and some of their N-substituted derivatives act as photographic developers. 'N,-N- diethyl pphenylenediamine is used as a photographic'developer in color photography.

We have now found new phosphono derivatives of oand p-arylenediamines and oand p-aminophenols, and have further 'found that these derivatives are efiicacious photographic developers.

It is, accordingly, an object of our invention to provide new arylenediamine and aminophenol derivatives and a process for the preparation thereof. A further object is to provide new photographic developing agents comprising these new derivatives. Other objects will become apparent hereinafter.

Our new arylamino compounds can be represented by the following general formulas:

and 1 wherein D represents an o or p-arylene group,"

- Our new arylamino compounds which. are derivatives of arylene diamine can be prepared reducing the appropriate azo compound. We have found that the reductions aremost advantageously accomplished by hydrogenating the nitro compounds in the presence of Raney nickel. Our

new arylamino compounds which are derivatives I of amino phenols can be prepared from the aforesaid phenylene-diamine derivatives by diazotization followed by hydrolysis of thediazonium salts, or by condensation. of aminophenols with chlorohydroxyalkane phosphonic acids.

The following examples will serve to illustrate of 1-.chloro-2-hydroxypropane-2-phosphonicacidand 285.6 g. (3.4 moles) of sodium carbonate were heated with vigorous stirring at 100 C. when no more carbon dioxide was evolved, the mixture was steam distilled to remove unchanged ethylaniline. To the residue was added sodium acetate and o-chlorobenzenediazonium sulfate until e. g. an 0- or p-phenylene group,- R represents an alkylene group, e. g. methylene or ethylene,

R1, R3 and R4 each represents hydrogen, or an alcohol radical, e. g. methyL'ethyl, n-propyl,-

isopropyl, cyclohexyl, benzyl, B-hydroxyethyl, pacetylethyl, carbethoxymethyl, furfuryl, etc., R2 represents hydrogen or an acyl group, e. g. acetyl or benzoyl, M represents hydrogen or arr alkali metal, X represents hydroxyl or amino and Q represents an oor p-arylene group, e. g. 0- or p-phenylene, attached directly" to which is a group of the following formula:

. I i O$Bs I r 0M; wherein M; represents hydrogen or alkali metal, R5 represents hydrogen or an acyl group, e. g.

acetyl or benzoyl, and R6 represents an alcohol radical.

a positive diaz'o test 'was obtained. The resulting azo dye was salted out and chargedwinto a shaking autoclave with 20 g.'of Raney nickel catalyst and 1000 cc. of methanol. The mixture was hydrogenated at C. until 2 moles of hydrogen per mole of dye were taken up. The reaction mixture was cooled and the catalyst filtered oil.

It was then steam distilled to remove methanol and o-chloroaniline. The resulting aqueous mixture was concentrated under reduced pressure to obtain the phosphono derivative which is white when pure, but is unstable in air and has no definite melting point.

y -phosphono-n-butyl) -p-phenylencdhmin ca om-0H HsNON on cm-cm-d cm on g. (1 mole) or ,B-hydroxyethylaniline, 226.3

' g. (1.2 moles) of 1-chloro-3-hydroxybutane-3- phosphonic acid and 285.6 g. (3.4 moles) of so-.

dium bicarbonate wereheated, with vigorous stirring, at 100 C. When no more carbon dioxide was evolved, the reaction was steam distilled and o-chlorobenzenedi'azonium sulfate until av positive diazo test was obtained. The resulting azo dye was salted out and charged into a shak- .ing autoclave with 20 g. of Raney nickel catalyst and one liter of methanol. The resulting mixture Was hydrogenated at 50 C; until 2 moles of hydrogen for each mole of azo dye was taken up. The cooled reaction mixture was filtered to remove the catalyst and was then steam distilled to remove methanol and o-chloroaniline. The aqueous residue was concentrated in vacuo to obtain the disodium salt of the phosphono derivative. The disodium salt was treated with the calculated amount of percent sulfuric acid to give the free phosphonic acid, a white crystalline compound which is unstable in air and possessing no definite melting point.

Example 3-N carbamidomethyl N (p hydroxy-s-phosphono-propyl) -2-methyl-p-phenylenediamine, dipotassium. salt I am 1 4 N/ on" CH:- -'CH:

I/OK o='1 163.1 g. (1 mole) of N-(m-tolyl) glycineamide, 275.2 g. (1.2 mole) of the dipotassium salt of 1-chloro-2-hydroxy propane-2-phosphonic acid and 120.1 g. (1.2 mole) of potassium bicarbonate were heated with vigorous stirring, at 100 C., until carbon dioxide was no longer evolved. The reaction mixture was 40 with g. of Raneynickel catalyst and 1000 cc. of methanol. The mixture was hydrogenated at 50 C. until 2'moles of hydrogen per mole of dye were taken up. The reaction mixture was filtered to remove the catalyst and then steam distilled to remove methanol and o-chloroaniline. The resulting aqueous residue was concentrated in vacuo to obtain the disodium salt of the phosphono derivative. The disodium salt was treated with 10 percent sulfuric acid to obtain the free phosphonic derivative, a white substance when pure, but unstable'in air and having no definite melting point.

Example 5N- (y-hydroxy- 'y zflwsphonon -butyl) -N-tetrahydrofurjuryl-p-aminophenol 1772 g. (1 mole) of N-tetrahydrofurfurylaniline, 226.3 g. (1.2 moles) of 1-ch1oro-3-hydroxylyst and then was steam distilled to remove'methanol and o-chloroaniline. The aqueous residue was concentrated in vacuo to obtain the dipotas- I sium salt of the phosphono derivative.

Example 4N,N-'di- (p-hydroxy-e-phosphonopropyl) -1,4-naphthalenediamine .f gillml to remove unchanged a-naphthylamine. To the residue was added sodium acetate ,and o-chlorobenzenediazonlum sulfate. until a positive diazo test was obtained. The resulting azo dye was When carbon dioxide was no longer evolved, the mixture was steam distilled 7 butane-3-phosphonic acid and 285.6 g. (3.4 moles) of sodium bicarbonate were heated with vigorous stirring at 100 C. When carbon dioxide was no longer evolved, the mixture was steam distilled to remove unchanged N-tetrahydrofurfurylaniline. To the residue'was added sodium acetate and o-chlorobenzenediazonium sulfate until a positive diazo test was obtained. The resulting azo dye was salted out and charged into a. shakingautoclave with 20 g. of Raney nickel catalyst and 1000 cc. of methanol. The mixture was hydrogenated at C. until 2 moles of hydrogen per mole of dye were taken up. The reaction mixture was filtered to remove the catalyst and then steam. distilled to remove methanol and salt of the phosphonoderivative of p-phenylenediamine. The disodium salt wa treated with 10 percent sulfuric acid to obtain the free phosphono derivative. 32.7 g. (0.1 mole) of the free phosphono derivative of p-phenylenediamine were dissolved in 300 cc. of water and ice with 30 g. of concentrated sulfuric acid. The mixture was diazotized with 7.2 g. of sodium nitrite. When diazotization was complete, the diazotized mixture was added to a boiling solution of 200 cc. of water in a closed system through which carbon dioxide was passed continuously. After about 30 minutes boiling, 5 g. of animal charcoal were added and the mixture was filtered. The filtrate was concentrated in vacuo to obtain the phosphone derivative of p-aminophenol, a white substance which is unstable in air and haszno definite melting point. 1

Example 6-N- ('y-hydroxyy -ph0sphonon -butyl) -o-aminophenol' .21.8 g. (0.2 mole) of o-ammopne ol, 14 g. (0.1

salted out and charged into a autoclave 10 mole) of l-chloro-3-hi lw -pholphonreacted o-aminophenol.

was made neutral to litmus with sulfuric acid and then concentrated in vacuo to obtain the 10 acid and 8.4 g. (0.1 mole) or sodium bicarbonate were heated in n-primary butanol until carbon dioxide was no longer evolved. The n-butanol was removed under reduced pressure. To the residue were added 100 cc. of water and 8.4 g. of 5 sodium bicarbonate. The resulting aqueous solution was extracted with ether to remove un- The aqueous residue phosphono derivative of o-aminophenol.

acetory a phosphonoethyl) -p phcnylenediamine, disodium salt A, CzHio CH: CHsCO O-- CH:

ONa

ONa 245.1 g. (1 mole) of m-(a-hydroxy a-phos phonoethyD-nitrobenzene were heated under ture was concentrated to drynessunder reduced pressure. The dry reaction product was mixed with 205 g. (2.5 moles) of fused sodium acetate. To the mixture was added, slowly with stirring at ordinary temperatures, 350 g. (2.5 moles) of s-methoxyethyl bromide. After addition of the 5 bromide, the mixture was heated for several hours on a steam bath. 7 The reaction'mixture was then steam distilled. The aqueous residue, containing N,N-di-(c-methoxyethyl) -m-(a-ace- The resulting solution was charged into a 35 261.1 g. (1 mole) of ni-(a-hydroxy-c-phosphonopropyl) -nitrobenzene were mixed with 106 e g. (1 mole) of sodium carbonate and enough water .to forms solution of the disodium salt of the phosphono derivative. The solution was charged into a shaking autoclavewith 20 g. of Raney nickel catalyst and the mixture was hydrogenatedat C. under 1500'pounds pressure. the reaction mixture was charged into an autoclave with 188.4g. (1.2 moles) of bromobenzene and 10 g. of active copper powder. The resulting mixture was heated at 220 to 240 C. for 24 hours. The reaction mixture was steam distilled to remove excess bromobenzene. The aqueous residue was concentrated somewhat in vacuo and the phenylated compound was separated from the aqueous portion-of the mixture. The phenylated compound was extracted with 5 percent hydrochloric acid to remove non-phenylated amino compound. The residue from the extraction was then coupled with o-chlorobenzenediazonium sulfate, using sodium bicarbonate to complete the coupling. The resulting azo dye was salted out and charged into a, shaking autoclave with 20 g. of Raney nickel catalyst and one liter (if-methanol. The mixture was hydrogenated at 50 C. until 2 moles of hydrogen for each mole of azo dye were taken up. The cooled mixture was filtered to remove catalyst and then steam distilled to remove methanol and o-chloroaniline. The resulting aqueous residue was concentrated in vacuo to obtain the disodium salt of the phosphono derivative of the phenylenediamine, a colorless compound of indefinite meltingpoint and unstable in air.

Example 9-1v ,1v diethyl s (Mammy-plies phonom'ethyZl-IA-diam*inonaphthalene 5'' v 4 y q -on (w I t. a... 283.1 g. (1 mole) of l-(hydroxy-phosphonomethyl) -8-nitronaphthalene were mixed with 106 g. (1 mole) of sodium carbonate and enough toxy-a-phosphonoethyl) .-a.minobe zene dis 5 aterto form a solution of the disodium salt of salt, was coupled with o-chlorobenzenediazonium sulfate, until a positive diazo test was obtained. The resulting azo dye was salted'out and charged into a shaking autoclave with 20 g. of Barley nickel and one liter of methanol. was hydrogenated at 50 C. until 2 moles of hydrogen per mole of -azo dye were taken up;

The cooled reaction mixturewas filtered to.re-

move the catalyst and then steam distilled to remove methanol and o-chloro aniline. The re- 60 suiting aqueous residue was concentrated in Y vacuo to obtain the salt of the phosphono' derivative of the phenylenediamine, a white compound of indefinite melting point and unstable in air. 65.

Example s- N -phenyl-z-(e hydrozy a phosphonopropyl) -p-phenylene-diam in e, disodium salt Y c 5 0 EN 2 a Q-H, CzHs-G-OH 0=P-0Na The mixture sure. The-nickel catalyst was filtered off and the reaction mixture was mixed with 390 g. (2.5 moles) of ethyl iodide and 132.5 g. (1.25 moles) of sodium' carbonate. The mixture was refluxed for several hours. To the cooled reaction mixture was added o-chlorobenzenediazonium sulfate until apositive diazo test was obtained. :The resulting azo dye was salted' out and charged into a shaking autoclave with 20 g. of Raney nickel catalyst and one liter of methanol. The

mixture was hydrogenated at 50 C. until 2 moles of hydrogen for each mole 'of am dye'were taken up. The cooled mixture was filtered to remove the catalyst and then steam distilled to remove methanol and o-chloroaniline. The resulting aqueous residue was concentrated in vacuo to obtain the disodium salt of the phosphono derivative or the 1,4-diaminonaphthalene, a colorless compound of indefinite melting point and 15 unstable in air. I 1

The nickelcatalyst was filtered of! and The solution was .derivative of N,N-diethyl-p-aminophenol,

Example 10-N,N-( Zi6thyl- 3 -(oz-hilldTOiBfl-aphosphonoethyl) -p-aminophenol 218.1 g. (1 mole) of o-(a-hydroxy-a-phosphonoethyl)phenol were placed in 1 liter of water containing 160 g. (4 moles) of sodium hydroxide. The mixture waswarmed until a'solutlon was obtained. The solution was cooled to C. and

- 1 mole of 'o-chlorobenzene diazonium sulfate were added. The resulting azo dye was salted out and.

charged into a shaking autoclave with 20 g. of

. Raney nickel and 1 liter of methanol. The mixture was hydrogenated at 50 C. until 2 molecular proportions of hydrogen for each molecular proportion of azo dye were taken up. The catalyst was filtered ofi and the reaction mixture steamdistilled to'remove methanol and o-chlorobenzene. aminophenol was salted out of the aqueous residue and washed first with cold 10 percent aqueous sodium sulfate and then with cold ethanol. 100 g. of the hosphono derivative thus obtained were charged into a shaking autoclave with 10 g. of Raney nickel and 500 cc. of ethanol. The autoclave was then heated at 220. to 240 C. for 30 hours. When cool, the reaction mixture was filtered to remove the nickel and the usual gelatin carriers, or in carriers, such as collodion, cellulose esters or resins. Those of our new phenylenediamine derivatives which are especially adapted to use in color hotography (see above) can be used to develop visible images from latent images in silver halide emulsions, or to develop-silver images from silver halide images V which are obtained-bya so-called reversal process or by rehalogenizinga visible silver image. When employed in connection. with color photography,

4 the "plr'enylenediamine derivatives act as de-..

velopers in the presence of couplers, and the oxidation products of the phenylenediamine derivatives, arising from the developing action, 'couple with the couplers or color-formers to give 55 colored bodies or dye. When used for the formation of colored photographic images, the phenylenediamine derivatives can be used in con-. junction with any well known coupler compounds, such as those described in Fischer U. S. 60

Patent 1,102,028, dated June 30, 1914; -Mannes and Godowsky U, S. Patent 2,108,602, dated.- February 15; 1938; Mannes, Godowsky and Peterson U. S. Patent 2,115,934, dated April 26, 1938, and Mannes, Godowsky and Peterson U. S. Patent.

2,126,337, dated August 9, 19'3s.

-All the arylenediamine derivatives described herein can be used for the purpose of producing black-andewhite. images from exposed photographic silver-halide emulsions. Developing solutions comprising our new arylenediamine derivatives can be made up in the usual manner,

sulfite and sodium carbonate.

The 1-chloro-2-hydroxypropane 2-phosphonic acid employed herein can be prepared from The 3-(a-hydroxy-a phosphonoethyl) -pchloroacetone according to the phosphonation process described by Conant-J. Am. Chem. Soc. 42, 833, 2337; 43, 1667; 44, 2530. The following example will serve to illustrate the preparation.

5 Example 1 1-1-Chl0ro-2-hydroa:ypropane- Z-phosphonic acid OH chem-$433, 10

To 92 g. (1 mole) of chloroacetone were slowly 'added 150 g. (1.1 moles) of phosphorous trichloride, at 10 to C. with stirring. 2 Care should be taken that the'reaction begins as soon as the addition of the phosphorous trichloride is started, as an accumulation of unreactedphos- 20 phorous trichloride may lead to an uncontrollable reaction. The reaction mixture should be protected from the moisture of the atmosphere, e. g.

by meansof a calcium chloride tube. 'The addition of phosphorous trichloride should be-made over a period of about 1.5 hours. After all theallowed to stand at about 20 C. for from 8 to 10 hours. At the end of this time, 298 g. (3.3 moles) of acetic acid is carefully added tothe reaction mixture over a three-hour period, with stirring and cooling to keep the reaction mixture at 20 to 25 C. .Protection from atmospheric moisture should be maintained. Afteraddition of the 5 acetyl acid, stirring, was continued for several hours. Then the reaction mixture was'distilled under reduced pressure to remove acetyl chloride. The residue of 1-chloro-2-hydr0xypropane-2 -phosphonic acid is a very viscous liquid 40 of amber color, which solidifies upon standing.

It needs no further purification. "l-chloro-3-hydroxybutane-3-phosphonic acid can be similarly prepared from fl-chloroethyl methyl ketone.

Thephosphonoalkyl nitro derivative employed in Examples '7, 8 and 9 can be prepared from nitroketones and nitroaldehydes as illustrated in the following examples.

nitrobenzene on -CHt O.==I OH To 165 g. (1 mole) of m-nitroacetophenone were added slowly 1'71 g. (1.25'moles) of phosphorous trichloride at a temperature of 75 to 85 C., with stirring. Stir'ring is somewhat diflicult at first, because of thefhigh melting point of the m nitroacetophenone, but as soon as 5 1 ,0 10 percent of the acid chloride has been added-the melting point is lowered enough so that there is obtained very efficient stirring. Care should be taken that there is no large amount of unreacted Phosphorous trichloride present in the reaction mixture until near the end of the addition. After the addition, stirring and heating .were continued for 5 to 6 hours. 7 Then, 225 g. (3.75 moles) of acetic acid-were added to the reaction mixture at to C. with efficient stirring and an efiective cold water-cooled condenser. Stirring was continued for 3 hours after 'the addition, at 75 to 85C. Then, the reaction 7 mixture was distilled under reduced pressure to Example 12m.-(a-Hydrozy-a phosphonoethyl) I I remove acetyl chloride.

3 cation. If desired, the produce can by pouring it while still liquid into a 5 percent aqueous hydrochloric acid the residue, and the 'andwashedtwicewith group, and tertiary blltfl 2,374,807 Theresidue was heated.

to about 100 C. in a good vacuum for a short time. The residue was a brown viscous liquid which soon solidified. It needs no further purifibe purified aqueous sodium chloride solution at 60 to 70C., with stirring. The phosphonated be separated from the aqueous liquors or be filtered ofl after it solidifies. In either case, it is advantageously washed with cold water before drying in the air. tone can be similarly phosphonated to give m- (a-hydroxy a phosphonopropyl) nitrobenzene, and 8-nitronaphthalene-1-a1dehyde can be similarly phosphonated to give 1-(hydroxy-phospho-' nomethyl) ii nitronaphthalene. The nitroketones can be prepared as described Syntheses, 10, 74.

The phosphono derivative employed in Example 10 can be prepared as illustrated in the following example:

Example 13-o-(a-Hydroxy-a-phosphonocthyl) phenol ('Ha .0H To 136 g. (1 mole) of o-hydroxyacetophenone were added, with stirring at 70 to 80 C., 295 g. (2.15 moles) of phosphoroustrichloride over a two-hour period. The reaction mixture was stirred at 70 to 80 eral hours.

(5.45 moles) a five-hour period. needed to keep the acetyl chloride irom volatilizing. The reaction mixture was stirred three further hours at 40 to 50 C. and the acetyl chloride was then distilled from-the reaction mixture under reduced pressure. One liter or 10 percent was then added to resulting suspension was heated with stirring at 75 to 85'. C. tor three hours. The oily layer wasseparated while hot To this mixture were added 327 g.

productis adarkbrownviscousliquidwhichsoon solidifies. It can be employed without further purification.

The term organi radical, which corresponds to an derived therefrom by dropping roup. a -rmfl i alcohol by dropping the OH group. henlyi is-do rived from benzyl alcohol by dro the OH is derived by 1 alcohol. r our invention derivative can it can m-Nitrophenyl ethyl ke-- hot water. The washedin Organic C. for 3 hours longer and then allowed to stand at 20 .to 25 C. for sev-- of acetic acid at to 'C. over An eflective condenser is.

alcohol radical. in accordance with .mistomaryusagaisintendedtomeanan c ancohol and is anddesiretof besecuredbyhetterslatentottheflnitedfltates w rollowin general tormula:

-Lay on wherein D represents an arylene .n .represents an alkylene group, member selected from the group consisting of group selected from the group consisting of oand p-aryiene groups, M represents a member selected from the group consisting of hydrogen and alkali metals, R1 represents a hydrogen and alcohol radicals, R4 represents an alcohol radical, and X represents a member selected from the group consisting of hydroxyl and amino groups.

2. An arylamino compound characterized by the following general formula:

R- -CH| wherein D represents a p-phenylene group, M represents a member selected from the group consisting 01 hydrogen and alkali metals, R represents an alkylene group, R1 represents an alcohol radical. v

3. An arylamino compound characterized by the following general formula:

formula:

cm. O onr-o-cn- 4 Ohio ONa a. An arylamlno compound or the following rormuls:

' cni-cneon on v CHPCHr-JJ-OE 011' Joann a. sums G. WY.

compound or the following 

